Reactions of epoxides (n → σ*)

Tyler W. Wilson, Scott E Denmark

Research output: Chapter in Book/Report/Conference proceedingChapter

Abstract

The primary mode of activation in chiral Lewis acid-catalyzed epoxide opening is polarization of the C-O σ-bond of the epoxide by coordination of a Lewis acid to the nonbonding electron pairs on the oxygen. Binding of the epoxide to the chiral Lewis acid activates the ring toward nucleophilic opening and places the enantiotopic carbons of the meso-epoxide within proximity to the influence of the chiral ligand on the Lewis acid. This chapter details the applications of chiral, nonracemic Lewis bases in the enantiodifferentiating reactions. In a detailed study on the mechanism of phosphoramide-catalyzed epoxide openings with SiCl4, Denmark and coworkers address questions regarding the stoichiometry, reaction kinetics, nonlinear effects, and the mode of activation for phosphoramide Lewis bases with SiCl4. The epoxide opening with SiCl4 produces an alkoxytrichlorosilane that can be susceptible to further Lewis base activation, leading to a dialkoxydichlorosilane and so forth.

Original languageEnglish (US)
Title of host publicationLewis Base Catalysis in Organic Synthesis
PublisherWiley-VCH Verlag
Pages1113-1151
Number of pages39
Volume3
ISBN (Electronic)9783527675142
ISBN (Print)9783527336180
DOIs
StatePublished - Aug 17 2016

Fingerprint

Epoxy Compounds
Lewis Acids
Lewis Bases
Chemical activation
Reaction kinetics
Stoichiometry
Carbon
Polarization
Oxygen
Ligands
Electrons

Keywords

  • 1-aza[6]helicenes
  • 1; 1'-biisoquinoline- N ; N -dioxide
  • 29Si NMR
  • 31 P NMR
  • Allenylphosphine oxides
  • BINAPO
  • BITIPIO
  • Bipyridyl- N -monooxide
  • Bromohydrin
  • Chlorohydrin
  • Co(salen) complex
  • Cooperative catalysis
  • Desymmetrization
  • Dual activation
  • Electrophilic activation
  • Epoxide
  • Epoxide opening
  • Fluorohydrin
  • Halogenation
  • Halohydrins
  • Hexacoordinate
  • Hydrohalogenation
  • Kinetic resolution
  • Meso-epoxides
  • Nonlinear effects
  • Nucleophilic activation
  • Organotin halides
  • Oxiranes
  • PINDOX
  • PINDY
  • Pentacoordinate
  • Phosphaferrocene
  • Phosphametallocene
  • Phosphine oxides
  • Phosphoramides
  • Pyridyl- N -oxides
  • Silicon tetrachloride
  • Siliconate

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Wilson, T. W., & Denmark, S. E. (2016). Reactions of epoxides (n → σ*). In Lewis Base Catalysis in Organic Synthesis (Vol. 3, pp. 1113-1151). Wiley-VCH Verlag. https://doi.org/10.1002/9783527675142.ch23

Reactions of epoxides (n → σ*). / Wilson, Tyler W.; Denmark, Scott E.

Lewis Base Catalysis in Organic Synthesis. Vol. 3 Wiley-VCH Verlag, 2016. p. 1113-1151.

Research output: Chapter in Book/Report/Conference proceedingChapter

Wilson, TW & Denmark, SE 2016, Reactions of epoxides (n → σ*). in Lewis Base Catalysis in Organic Synthesis. vol. 3, Wiley-VCH Verlag, pp. 1113-1151. https://doi.org/10.1002/9783527675142.ch23
Wilson TW, Denmark SE. Reactions of epoxides (n → σ*). In Lewis Base Catalysis in Organic Synthesis. Vol. 3. Wiley-VCH Verlag. 2016. p. 1113-1151 https://doi.org/10.1002/9783527675142.ch23
Wilson, Tyler W. ; Denmark, Scott E. / Reactions of epoxides (n → σ*). Lewis Base Catalysis in Organic Synthesis. Vol. 3 Wiley-VCH Verlag, 2016. pp. 1113-1151
@inbook{116c9acf4dd2401b969406c11e46455c,
title = "Reactions of epoxides (n → σ*)",
abstract = "The primary mode of activation in chiral Lewis acid-catalyzed epoxide opening is polarization of the C-O σ-bond of the epoxide by coordination of a Lewis acid to the nonbonding electron pairs on the oxygen. Binding of the epoxide to the chiral Lewis acid activates the ring toward nucleophilic opening and places the enantiotopic carbons of the meso-epoxide within proximity to the influence of the chiral ligand on the Lewis acid. This chapter details the applications of chiral, nonracemic Lewis bases in the enantiodifferentiating reactions. In a detailed study on the mechanism of phosphoramide-catalyzed epoxide openings with SiCl4, Denmark and coworkers address questions regarding the stoichiometry, reaction kinetics, nonlinear effects, and the mode of activation for phosphoramide Lewis bases with SiCl4. The epoxide opening with SiCl4 produces an alkoxytrichlorosilane that can be susceptible to further Lewis base activation, leading to a dialkoxydichlorosilane and so forth.",
keywords = "1-aza[6]helicenes, 1; 1'-biisoquinoline- N ; N -dioxide, 29Si NMR, 31 P NMR, Allenylphosphine oxides, BINAPO, BITIPIO, Bipyridyl- N -monooxide, Bromohydrin, Chlorohydrin, Co(salen) complex, Cooperative catalysis, Desymmetrization, Dual activation, Electrophilic activation, Epoxide, Epoxide opening, Fluorohydrin, Halogenation, Halohydrins, Hexacoordinate, Hydrohalogenation, Kinetic resolution, Meso-epoxides, Nonlinear effects, Nucleophilic activation, Organotin halides, Oxiranes, PINDOX, PINDY, Pentacoordinate, Phosphaferrocene, Phosphametallocene, Phosphine oxides, Phosphoramides, Pyridyl- N -oxides, Silicon tetrachloride, Siliconate",
author = "Wilson, {Tyler W.} and Denmark, {Scott E}",
year = "2016",
month = "8",
day = "17",
doi = "10.1002/9783527675142.ch23",
language = "English (US)",
isbn = "9783527336180",
volume = "3",
pages = "1113--1151",
booktitle = "Lewis Base Catalysis in Organic Synthesis",
publisher = "Wiley-VCH Verlag",
address = "Germany",

}

TY - CHAP

T1 - Reactions of epoxides (n → σ*)

AU - Wilson, Tyler W.

AU - Denmark, Scott E

PY - 2016/8/17

Y1 - 2016/8/17

N2 - The primary mode of activation in chiral Lewis acid-catalyzed epoxide opening is polarization of the C-O σ-bond of the epoxide by coordination of a Lewis acid to the nonbonding electron pairs on the oxygen. Binding of the epoxide to the chiral Lewis acid activates the ring toward nucleophilic opening and places the enantiotopic carbons of the meso-epoxide within proximity to the influence of the chiral ligand on the Lewis acid. This chapter details the applications of chiral, nonracemic Lewis bases in the enantiodifferentiating reactions. In a detailed study on the mechanism of phosphoramide-catalyzed epoxide openings with SiCl4, Denmark and coworkers address questions regarding the stoichiometry, reaction kinetics, nonlinear effects, and the mode of activation for phosphoramide Lewis bases with SiCl4. The epoxide opening with SiCl4 produces an alkoxytrichlorosilane that can be susceptible to further Lewis base activation, leading to a dialkoxydichlorosilane and so forth.

AB - The primary mode of activation in chiral Lewis acid-catalyzed epoxide opening is polarization of the C-O σ-bond of the epoxide by coordination of a Lewis acid to the nonbonding electron pairs on the oxygen. Binding of the epoxide to the chiral Lewis acid activates the ring toward nucleophilic opening and places the enantiotopic carbons of the meso-epoxide within proximity to the influence of the chiral ligand on the Lewis acid. This chapter details the applications of chiral, nonracemic Lewis bases in the enantiodifferentiating reactions. In a detailed study on the mechanism of phosphoramide-catalyzed epoxide openings with SiCl4, Denmark and coworkers address questions regarding the stoichiometry, reaction kinetics, nonlinear effects, and the mode of activation for phosphoramide Lewis bases with SiCl4. The epoxide opening with SiCl4 produces an alkoxytrichlorosilane that can be susceptible to further Lewis base activation, leading to a dialkoxydichlorosilane and so forth.

KW - 1-aza[6]helicenes

KW - 1; 1'-biisoquinoline- N ; N -dioxide

KW - 29Si NMR

KW - 31 P NMR

KW - Allenylphosphine oxides

KW - BINAPO

KW - BITIPIO

KW - Bipyridyl- N -monooxide

KW - Bromohydrin

KW - Chlorohydrin

KW - Co(salen) complex

KW - Cooperative catalysis

KW - Desymmetrization

KW - Dual activation

KW - Electrophilic activation

KW - Epoxide

KW - Epoxide opening

KW - Fluorohydrin

KW - Halogenation

KW - Halohydrins

KW - Hexacoordinate

KW - Hydrohalogenation

KW - Kinetic resolution

KW - Meso-epoxides

KW - Nonlinear effects

KW - Nucleophilic activation

KW - Organotin halides

KW - Oxiranes

KW - PINDOX

KW - PINDY

KW - Pentacoordinate

KW - Phosphaferrocene

KW - Phosphametallocene

KW - Phosphine oxides

KW - Phosphoramides

KW - Pyridyl- N -oxides

KW - Silicon tetrachloride

KW - Siliconate

UR - http://www.scopus.com/inward/record.url?scp=85018287225&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85018287225&partnerID=8YFLogxK

U2 - 10.1002/9783527675142.ch23

DO - 10.1002/9783527675142.ch23

M3 - Chapter

AN - SCOPUS:85018287225

SN - 9783527336180

VL - 3

SP - 1113

EP - 1151

BT - Lewis Base Catalysis in Organic Synthesis

PB - Wiley-VCH Verlag

ER -